US6559264B1 - Malonic acid ester/triazole mixed blocked HDI trimer/formaldehyde stabilization - Google Patents
Malonic acid ester/triazole mixed blocked HDI trimer/formaldehyde stabilization Download PDFInfo
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- US6559264B1 US6559264B1 US09/857,087 US85708701A US6559264B1 US 6559264 B1 US6559264 B1 US 6559264B1 US 85708701 A US85708701 A US 85708701A US 6559264 B1 US6559264 B1 US 6559264B1
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- Prior art keywords
- blocked
- isocyanate groups
- equivalent
- aliphatic
- cycloaliphatic polyisocyanate
- Prior art date
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- Expired - Fee Related
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- WRSJXZXHTNVUGT-UHFFFAOYSA-N C.CC1CC(C)(C)NC(C)(C)C1 Chemical compound C.CC1CC(C)(C)NC(C)(C)C1 WRSJXZXHTNVUGT-UHFFFAOYSA-N 0.000 description 3
- FRUWUOBXYGYINS-UHFFFAOYSA-N C.CNNC(C)=O Chemical compound C.CNNC(C)=O FRUWUOBXYGYINS-UHFFFAOYSA-N 0.000 description 3
- MSGFTHUDDIBEMG-UHFFFAOYSA-N CC(O)COC(=O)NNC(=O)OCC(C)O Chemical compound CC(O)COC(=O)NNC(=O)OCC(C)O MSGFTHUDDIBEMG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/006—Polymeric products of isocyanates or isothiocyanates with aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
- C09K15/22—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen containing an amide or imide moiety
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- the present invention relates to blocked polyisocyanate crosslinking agents, to the production thereof and to the use thereof in single-component stoving lacquers, particularly OEM clear lacquers (original equipment material, initial lacquer coating).
- blocked polyisocyanates are used as additives which impart improvements to single-component stoving lacquers which are used in the lacquer coating of automobiles.
- the stringent requirements of improved lacquer technology properties can be fulfilled relatively satisfactorily by blocked polyisocyanates.
- the most important industrial lacquer polyisocyanates are based on 1,6-diisocyanatohexane (HDI).
- the available blocking agents for polyisocyanates on an industrial scale when maximum deblocking temperatures of 140° C. are required are malonic esters and 1,2,4-triazole.
- a combination of HDI-based polyisocyanates with malonic esters or 1,2,4-triazole, or, as shown in the comparative example given later, with a malonic ester/1,2,4-triazole mixture does not result in a usable liquid lacquer crosslinking agent which is stable on storage, because these products crystallise out.
- the tendency of HDI polyisocyanates blocked with malonic ester to crystallise is already known from EP-A 600 314, and that of triazole-blocked polyisocyanates is known from EP-A 654 490 and 741 157.
- the object of the present invention was to modify polyisocyanates which are based on HDI and which are blocked with mixtures of malonic ester and 1,2,4-triazole, in order to form liquid crosslinking agents, which do not crystallise in solvents, for single-component stoving lacquers.
- the present invention relates to aliphatic and/or cycloaliphatic polyisocyanates, wherein
- the present invention also relates to a method of producing the non-crystallising blocked polyisocyanates according to the invention from
- the non-crystallising, blocked polyisocyanates according to the invention preferably have a content of stabilisers against thermal yellowing amounting to
- HALS amines comprising a structural unit of formula (II).
- Stabilisers of this type are known from EP-A-829 500, for example.
- the present invention relates to the use of the blocked polyisocyanates according to the invention as crosslinking agents for organic polyhydroxyl compounds in polyurethane stoving lacquers, for example for automobile clear lacquers.
- a content of formaldehyde is an essential feature of the invention for the claimed polyisocyanate crosslinking agents. Surprisingly, formaldehyde exhibits two modes of action:
- paraformaldehyde are preferably used per 100 equivalent % of blocked polyisocyanate, and are incorporated by reaction by means of a catalyst such as Na methylate, for example. This is equivalent to about 0.8 to 5.0% by weight of formaldehyde with respect to the blocked polyisocyanate.
- a formaldehyde content of 2.0 to 3.0% by weight with respect to the blocked polyisocyanate is most particularly preferred.
- the polyisocyanate component is placed in a reaction vessel, optionally together with a little solvent, e.g. 1-methoxy-2-propyl acetate (MPA), at about 50° C., the acidic CH ester, e.g. malonic ester, is added thereto as a mixture with about 2% of a 30% Na methylate solution and is reacted at 70-90° C. to give the calculated NCO content. Thereafter, the calculated amount of 1,2,4-triazole is added, dissolved in further MPA, and is reacted out at about 90° C. so that NCO can no longer be detected. The batch is cooled to about 45° C.
- a little solvent e.g. 1-methoxy-2-propyl acetate (MPA)
- MPA 1-methoxy-2-propyl acetate
- the polyisocyanates on which the blocked polyisocyanates according to the invention are based are known lacquer polyisocyanates which comprise aliphatically and/or cycloaliphatically and/or aromatically bonded isocyanate groups and which have an isocyanate content of 7 to 30, preferably 12 to 25% by weight.
- the polyisocyanates which are preferably used are lacquer polyisocyanates known in the art, which comprise biuret, isocyanurate, urethane, allophanate and/or uretdione groups and which are based on 1,6-diisocyanatohexane (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) and/or bis-(4-isocyanatocyclohexyl)-methane (H 1 2 MDI or Desmodur W®/Bayer AG).
- HDI 1,6-diisocyanatohexane
- IPDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
- H 1 2 MDI or Desmodur W®/Bayer AG bis-(4-isocyanatocyclohexyl)-methane
- lacquer polyisocyanates which are trimerised asymmetrically, and which therefore comprise iminooxadiazinedione groups in addition to isocyanurate, and which are based on 1,6-diisocyanatohexane can also be used, such as those described in EP-A 798 299 for example.
- Polyisocyanates based on other isocyanates can also be used, such as those based on diisocyanatobutane-1,4, 2,4- or 2,6-diisocyanato-1-methyl-cyclohexane, 2,5- and/or 2,6-bis-isocyanato-norbornane, 3- and/or 4-isocyanatomethyl-1-methylcyclohexane, 1,4-bis-(2-isocyanato-prop-2-yl)-benzene, 1,3-diisocyanatomethylbenzene, or 1,3- or 1,4-bis-isocyanatomethylcyclohexane, for example.
- the substances which are most particularly preferred as the polyisocyanate component are polyisocyanates which comprise isocyanurate and which are based on 1,6-diisocyanatohexane.
- the substances which are used as the blocking component firstly comprise acidic CH esters, for example diethyl malonate or ethyl acetate and/or methyl, isopropyl, isobutyl or tert.-butyl derivatives thereof. Diethyl malonate is preferred.
- 1,2,4-triazole is used in said blocking mixture, 1,2,4-triazole is produced on a large scale industrially from 1 mole of hydrazine hydrate and at least 2 moles of formamide.
- the acidic CH ester and triazole can each be used in amounts of 5-95 equivalent %, preferably 20-80 equivalent %.
- oximes such as butanone oxime for example, secondary amines e.g. diisopropylamine, acidic NH heterocycles, such as imidazole or 3,5-dimethylpyrazole for example, or lactams e.g. ⁇ -caprolactam.
- the stabilisers which are known from EP-A 0 829 500 can be used as additional stabilising components.
- the substance which is preferred in this connection is the hydrazide of formula (Ia)
- the solvents which can be used are those which are known from polyurethane chemistry and which are inert to NCO groups, for example 1-methoxy-2-propyl acetate, solvent naphtha 100 or butyl acetate. If the NCO groups are blocked, alcohols e.g. isobutanol are also preferably used in order to facilitate transesterification with the alcohol residues of the blocking agents.
- This mixture-blocked polyisocyanate was stabilised with 3.0% of formaldehyde with respect to the solids content of the blocked polyisocyanate.
- the polyisocyanate and methoxypropyl acetate were placed in a reaction vessel and heated to about 50° C.
- the mixture of malonic ester and 1.2 g Na methylate solution (as a 30% solution in methanol) were added to this stirred solution and the batch was subsequently stirred for 2 hours at 70° C. until the NCO content was less than the calculated value of 7.6%.
- the colourless flakes of triazole were then added thereto, the internal temperature was raised to 90° C. and the batch was subsequently stirred for about 3 hours until NCO groups could no longer be detected.
- the batch was cooled to about 45° C.
- Example 2 The nature and amounts of substances used in this example were the same as in Example 1, with the exception that modification of the blocked polyisocyanate with formaldehyde was omitted. This resulted in a product which started to crystallise out after storage for one week at room temperature. This blocked polyisocyanate thus cannot be used in single-component lacquer formulations which are stable on storage.
- This mixture-blocked polyisocyanate was stabilised with 2.7% of stabilisers with respect to the solids content of the blocked polyisocyanate.
- two further stabilisers (see EP-A 829 500 A2) were admixed with the blocked polyisocyanate solution, namely 2.0% of a hydrazide as mentioned above and 1.0% of a HALS amine.
- the polyisocyanate and methoxypropyl acetate were placed in a reaction vessel.
- the mixture of diethyl malonate with about 2%, i.e. 2.4 g, of Na methylate solution (a 30 % solution in methanol) were added in portions at about 50° C., with stirring.
- the temperature was raised to 70° C. and the batch was stirred for about 11 ⁇ 2 hours until the NCO content was less than the calculated value of 5.95%.
- the colourless flakes of triazole were then added thereto, the temperature was raised to 90° C. and the batch was subsequently stirred for about 3 hours until NCO groups could no longer be detected (IR spectrum).
- the batch was cooled to 45° C.
- the crosslinking agent from Example 3 was mixed with the following components to give a clear lacquer.
- This clear lacquer was applied to test panels which were coated with a commercially available base lacquer, e.g. that supplied by Spies & Hecker of Cologne, to give a wet coat thickness of about 120 to 150 ⁇ m, and were stoved and tested as explained in the following Table.
- pendulum damping (oscillations) 1) 143 (s) 200 resistance to solvents (ranking*) 2) (X/MPA/EA/AC) 1 min 1234 5 min 2244 resistance to chemicals (° C.) 3) (gradient oven method) resin 36 brake fluid 36 pancreatin, 50% 36 NaOH, 1% 36 H 2 SO 4 , 1% 41 FAM: 10 min. (ranking*) 2 thermal yellowing 4) clear lacquer on LM base lacquer initial yellowing (b) 0.1 yellowing after over-stoving for 30 min at 1.9 160° C. ( ⁇ b) clear lacquer on H 2 O base lacquer initial yellowing (b) ⁇ 1.2 yellowing after over-stoving for 30 min at) 1.2 160° C. ( ⁇ b) scratch-resistance (laboratory washing train) 5) initial 20° gloss 90.8 loss in gloss after 10 washing cycles 23.2 *)0 - good; 5 - poor
- the system according to the invention exhibits good lacquer properties as a whole.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Steroid Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Liquid Crystal Substances (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19856412 | 1998-12-07 | ||
DE1998156412 DE19856412A1 (de) | 1998-12-07 | 1998-12-07 | Verfahren zur Koagulation wäßriger PUR-Dispersionen die reaktives oder nachvernetzbares Polyurethan dispergiert enthalten, so erhaltene Produkte und deren Verwendung |
DE19856968 | 1998-12-10 | ||
DE1998156968 DE19856968A1 (de) | 1998-12-10 | 1998-12-10 | Malonester/Triazolmischblockiertes HDI-Trimerisat/Formaldehydstabilisierung |
PCT/EP1999/009069 WO2000034356A1 (de) | 1998-12-07 | 1999-11-24 | Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung |
Publications (1)
Publication Number | Publication Date |
---|---|
US6559264B1 true US6559264B1 (en) | 2003-05-06 |
Family
ID=26050609
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/857,087 Expired - Fee Related US6559264B1 (en) | 1998-12-07 | 1999-11-24 | Malonic acid ester/triazole mixed blocked HDI trimer/formaldehyde stabilization |
US09/857,537 Expired - Fee Related US6451963B1 (en) | 1998-12-07 | 1999-11-24 | Method of coagulating aqueous PUR dispersions containing dispersed therein reactive or secondary cross-linked polyurethane, the products obtained thereby and their use |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/857,537 Expired - Fee Related US6451963B1 (en) | 1998-12-07 | 1999-11-24 | Method of coagulating aqueous PUR dispersions containing dispersed therein reactive or secondary cross-linked polyurethane, the products obtained thereby and their use |
Country Status (19)
Country | Link |
---|---|
US (2) | US6559264B1 (es) |
EP (2) | EP1141070B1 (es) |
JP (2) | JP4916048B2 (es) |
KR (2) | KR100549762B1 (es) |
CN (2) | CN1156505C (es) |
AT (2) | ATE226221T1 (es) |
AU (2) | AU1654000A (es) |
BR (2) | BR9915981B1 (es) |
CA (2) | CA2353412C (es) |
DE (2) | DE59907571D1 (es) |
ES (2) | ES2185409T3 (es) |
HK (2) | HK1042907A1 (es) |
HU (1) | HUP0104571A3 (es) |
ID (1) | ID30165A (es) |
IL (2) | IL142924A0 (es) |
PL (1) | PL200857B1 (es) |
PT (1) | PT1141070E (es) |
TR (1) | TR200101655T2 (es) |
WO (2) | WO2000034356A1 (es) |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040067318A1 (en) * | 2001-01-12 | 2004-04-08 | Jones Richard Garfield | Mixed-blocked polyisocyanates and uses thereof |
US20070249746A1 (en) * | 2006-04-08 | 2007-10-25 | Thorsten Rische | Microporous coating based on polyurethane polyurea |
US20070259984A1 (en) * | 2006-05-04 | 2007-11-08 | Bayer Materialscience Ag | Microporous coating based on polyurethane polyurea |
US20110082226A1 (en) * | 2009-10-01 | 2011-04-07 | Industrial Technology Research Institute | Multi-isocyanate prepolymer |
WO2012054616A2 (en) | 2010-10-20 | 2012-04-26 | Bioformix, Llc | Synthesis of methylene malonates substantially free of impurities |
WO2013059473A2 (en) | 2011-10-19 | 2013-04-25 | Bioformix Inc. | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom |
US9108914B1 (en) | 2013-01-11 | 2015-08-18 | Sirrus, Inc. | Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway |
US9181365B2 (en) | 2012-03-30 | 2015-11-10 | Sirrus, Inc. | Methods for activating polymerizable compositions, polymerizable systems, and products formed thereby |
US9217098B1 (en) | 2015-06-01 | 2015-12-22 | Sirrus, Inc. | Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound |
US9234107B2 (en) | 2012-03-30 | 2016-01-12 | Sirrus, Inc. | Ink coating formulations and polymerizable systems for producing the same |
US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
US9279022B1 (en) | 2014-09-08 | 2016-03-08 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
US9315597B2 (en) | 2014-09-08 | 2016-04-19 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
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US9416091B1 (en) | 2015-02-04 | 2016-08-16 | Sirrus, Inc. | Catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
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